Ureids and thioureids.



BERNHARD HEYMANN, or-wrnsnonr-oN-THE-NrEnERRHEIN, RICHARD KOTHE, or

OPLADEN, NEAR COLOGNE, OSKAR DRESSEL, or MI'TLHEIM, NEAR COLOGNE, AND

ANTON OSSENBECK, OF COLOGNE, GERMANY, .ASSIGN'ORS T0 SYNTHETIC PATENTS co., INC, on NEW YORK, N. Y., A CORPORATION or NEW YORK.

UREIDS AND THIOUBEIDS.

No Drawing.

To all whom, it may concern."

Be it known that we, BERNHARI) HEY- MANN, RICHARD KoTHE, OSKAR DRnssEL, and ANTON OSSENBECK, citizens of the German Empire, residing at, respectively, Wiesdorfon-the-Niederrhein; Opladen, near Cologne;

of aromatic substances substituted in the amino group by means of nitro derivatives of the aromatic acidyl halids, of aromatic sulfo acids, etc., reduction to the corresponding amino products and finally condensation of these substances to ureid compounds such as ureids, thioureids, etc.

These substitution derivatives of amino derivatives of aromatic substances may be again substituted by the above acidyl halids, reduced and condensed to furnish the ureids, thioureids, etc.

The ureids, thioureids, etc., of these substituted amino derivatives of aromatic sub-. stances are characterized by containing in their molecule an aggregation of the group.

in which A stands for the aryl radical of an aromatic substance such as phenyl, tolyl, diphenyl, ditolyl, naphthyl, carbazyl, anthracyl, etc., in the formof their sulfo acid derivatives and which may further contain substituting groups,' such as hydroxyl OH, halogen-C1, Br, and L'the carboXyl-, etc., R stands for the residue of an acid group such as CO, the residue of the carboxyl group; CS, the'residue of the thiocarboXyl group; O the residue of the sulfonic group, etc.; and Y for'an aromatic radical, such as phenylene C H,,, naphthylene C, H and their derivatives.

As starting material the amino derivatives ofaromatic substances may be-employed in the form of their mono-, di-, or higher sulfonated derivatives, which may be further substituted, such as for example, aminobenzoic-sulfoacids and their derivatives,

Specification of Letters Patent.

derivatives, amino-carbazol-sulfonic acids,

aminonaphtholor naphthylamin sulfonic acids, etc. These-amino derivatives of aromatlc substances are substituted by nitro derivatives of aromatic acidyl halids, such as para-nitro-benzoyl chlorid, meta nitrobenzoyl-chlorid of the formula:

ratentearraaiaiaia Application filed December 17,1914. Serial No. 877,683. Y

meta-nitroanisoyl-chlorid, etc., or by nitrobenzene-sulfonyl-chlorid of the formula:

or by para nitro-phenyl urea-chlorid of the formula: v v

OSHA N0 or by l-nitro-naphthalene-5-sulfonyl-chlorid of the formula formula:

m oo-c1 The reduction of thesesubstituted amino substances is carried out by means of iron' and hydrochloric acid or by any other appropriate method furnishing products of the following general formula:

Finally these amino. derivatives of the substituted amino substances are treated with phosgen, bisulfid of carbon, etc., to furnish the corresponding ureids, thioureids, etc.

For this condensation with phosgen, bisulfid of carbon, etc., we may employ two inole'- cules of the same substituted amino substances described above with the general formula or we may employ one molecule each of different substituted amino sub'stances included in the above general formula.

We may also employ for this reaction with phosgen, bisulfid of carbon, etc., one molecule of a substituted amino substance described above and one molecule of the substituted aminonaphthalene substance described in our United States patent application Serial No. 846195, filed June 19, 1914'. Therefore, if the condensation is carried out with phosgen, we would obtain ureids with the following general formula: 10

in which the radicals used in the formula are to be defined as above and aryl means an aromatic radical different from A, such as phenyl -G H naphthyl (1 11,, etc., 'or substitution products thereof;

and if the reaction is carried 'out with bisulfid of carbon, we would obtain thioureids with the following general formula under the above definition of the radicals:

The ureids and thioureids so obtained have the following general formula wherein Z represents a metalloid, particularly oxygen or sulfur If, as above stated, the acid haloids are repeatedly introduced into the amino substances, derivatives of the following general formula areobtained: V

A-NH-R-Y-NH R -Y Nn which upon treatment with phosgen furnish 3o ureids of the following general formula:

In'the same manner three, four, or still more molecules of the acid haloids might be introduced into the amino substances and substitucorrespondingly more complicated and thiotion derivatives and finally ureids ureids, etc., are obtained.

In all these general formulae R stands for I a residue of an acid group.

For the formation of the substituted amino substances nitro derivatives of various acid haloids may be employed, sothat in the general formula last given one B may stand for -CO and the other for SO if nitrobenzoy'lchlorid and nitroaryl-sulfonyl-chlobenzoylchlorid on meta-aminobenz'oylaminosulfonyl-salicylic acid and subsequent reduction are dissolved'by addition of the necessary quantity of sodium carbonate to form the neutral salt. Then 50 parts of crystallized acetate ofsodium are added and while stirring phosgen is introduced. The reaction is finished if on addition of nitrite and HCl no diazotation takes place any more. Most of the ureid separates during the operation, which separation is completed by addition of common salt. By dissolving the ureid in sodium carbonate and saltingit out again the neutral sodium salt is obtained as a white precipitate. The new compound thus obtained has in a free state most probably the following formula:

It forms salts with metals and shows strong blood parasite destroying qualities. we

Example 2: 63.9 parts of the acid sodium salt of the aminoanisoyl-aminoanisoyl-lamino-S-naphthol-fidisulfonic acid and 49.3 parts of the acid sodium salt of the metas aminobenzoyl meta amino benzoyl-aminosulfonyl-salicylic acid are mixed and dissolved by addition of sodium carbonate to form the neutral salt. Then 100 parts of crystallized sodium acetate are added and While stirring phosgen is introduced into this solution until on addition of nitrite and HUI no diazotation takes place any more. The product of the reaction is isolated as is indicated in Example 1. The new acid thus obtained has in a free state most probably the following formula:

Example 3: 56.5 parts of the acid sodium salt obtained by the action of para-nitrobenzoyl chlorid upon l-aminonaphthalene- 3.6-disulfonic acid, subsequent reductionand SOaH introduction of the meta-nitro-benzoyl residue into the resulting acid and subsequent reduction and in'the free acid form having the formula SO3H- -SOQH Ml l are dissolved in Water and carbonate of soda to form the neutral salt. Then 50 parts of calout again, it is obtained as a White precipitate.

Example 4: 62.5 parts of the acid sodium salt obtained by the action of nitroanisoylchlorid on the reduced substituted derivative obtained from nitroanisoylchlorid and laminonaphthalene-4=.6-disulfonic acid and 40 subsequent reduction which possesses the following formula:

cined sodium carbonate are added and phosgen 1s lntroducedas 1n Example 1. The reac- Liz:

tion is finished, if on addition of nitrite of sodium to an acidulated test portion no diathol-3.6-disulfonic acid and subsequent re-- By dissolving the same with the addition of carbonate of soda and precipitating it by chlorid of sodium the neutral salt is obtained which is easily soluble in water. In the dry form the neutral salt is a faintly reddish powder. It forms azo dyes with diazobenzene.

Example 6: 63 parts of the acid sodium are dissolved in 1000 parts of water and Lemma zotation takes place any more. The new acid thus obtained has the following formula:

duct-ion which possesses the following for- EH OH- soafi i som salt of the substitution derivative obtained by condensation of para-nitrocinnamylchlorid with the product of the reaction of para-nitr0-cinnamylchlorid on 1.8-aminonaphthol-4:.6-disulfonic acid and subsequent reduction which has the following constitution:

crystallized sodium carbonate are added treated with carbonate of soda, until the and while stirring phosgen is introduced in neutral salt is formed. Then 50 parts of a slow current at a temperature of 40-45" C.

The treatment with phosgen is continued until an acidulated test sample shows no reaction with nitrate which means that there is no amino substance present any more. Already during the operation the ureid NH- lo I CH=CH-CO are dissolved in water and carbonate of soda to form the neutral salt. Then 50 parts of calcined sodium carbonate are added and phosgen is introduced. The reaction is finished, if on addition ofnitrate of sodium no diazot'ation takes place any more. The new acid thus obtained has the following forf Y i J J Owo-i /U /Nfi SOBH SO33 By dissolving the acid in' carbonate of soda 40 and salting it out again, it is obtained as a yellowish precipitate. r I I In a like manner ureas with similar properties are obtained if other sulfonic acids such as l-amino-S-methoxy-fi-disulfonic separates for the greatest part. After the end of the reaction chlorid of sodium is added in order to complete the separation. The free acid has the following constitution:

cn =cH-oo \NH I I I CH=CHCO 3033 OH NH som 2.8.3.6-aminonaphthol disulfonic acid are employed.

Example 7 61 parts of the acidsodium salt obtained by the action of meta-nitrobenzoylchlorid on the reduced substituted derivative obtained from metanitrobenzoylchlorid and 1-a1nino-8-cthoxynaphtha]one-3.6-disulfonic acid and subsequent reduction which possesses the following formula:

acid are employed; or if instead of the aminoacidyl groups of the examples other acidyl radicals are introduced, such as aminophenyl-acetic-acid-chlorid. The same or different acidyl radicals or aminonaphthalene compounds can be used.

Although we have above described examples by which the ureids and thioureids,

etc., may be obtained, nevertheless, we do ing equivalents for the ingredients, or the operations employed in the process. It is probable that substitutes, for example, various kinds of aminobenzol derivatives, various aromatic acidyl halids and of aromaticsulfo acids, etc., may be employed without departing from the scope of the invention intended to be secured hereby.

1. As new products'ureid compounds of substituted amino derivatives of aromatic substances characterized by containing in their molecule the general group:

A NHRY-NH I in which A stands for the monovalent aryl radical of an aromatic substance containing a sulfo group, R stands for the residue of an not wish to be understood as thereby exclud acid group, and Y for an aromatic radical contalning no substituted amino groups, substantially as described.

2. As new products ureid compounds of substituted amino derivatives of aromatic substances characterized by containing in their molecule the general group:

in which A stands for the monovalent aryl radical of an aromatic substance containing a sulfo group, and Y for an aromatic radical containing no substituted amino groups, sub stantially as described.

3. Asncw products ureid compounds of substituted amino derivatives of aromatic substances characterized by containing in their molecule the general group:

in which A stands for the aryl radical of an aromatic substance containing a sulfo group, substantially as described.

el. As new products ureid compounds of substituted amino derivatives of aromatic substances characterized by containing in their molecule the general group:

in which A stands for the aryl radical of an aromatic substance containing a sulfo group, substantially as described.

5. As new products ureid compounds of substituted amino derivatives of aromatic substances characterized by containing in their molecule the general group:

substantially as described.

6. As new products ureid compounds of substituted amino derivatives of aromatic substances characterized by containing in their molecule the general group:

substantially as described.

7 As new products ureid compounds of substituted amino derivatives of aromatic substances characterized by the following formula:

in which A stands for the aryl radical of an aromatic substance containing a sulfo group, R stands for the residue of an acid group, and Y for :u: aromatic radical, Z standing for a metalloid, aryl standing for any aromatic radical, forming salts with metals, substantially as described.

9. As new products ureid compounds of substituted amino derivatives of aromatic substances characterized by the following formula:

in which A stands for the aryl radical of an aromatic substance containing a sulfo group, R stands for the residue of an acid group, and Y for an aromatic radical, Z standing for oxygen or sulfur, aryl standing for any aromatic radical, forming salts with metals, substantially as described.

10. As new products ureid compounds of substituted amino derivatives of aromatic substances characterized by the following formula:

in which A stands for the aryl radical.of an aromatic substance containing a sulfo group, R stands for the residue of an acid group,

and Y for an aromatic radical, Z standing for oxygen or sulfur, forming salts with metals. substantially as described.

11. As new products ureids of substituted amino derivatives of aromatic substances characterized by the following formula:

in which A stands for the aryl radical of an aromatic substance containing a sulfo group, R stands for the residue of an acid group, and Y for an aromatic radical, forming salts with metals, substantially as described.

12. As new products ureids of substituted amino derivatives of aromatic substances in which A stands for the aryl radical of w an aromatic substance containing a sulfo group, R stands for the residue of an acid group, and Y for an aromatic radical, forming salts with metals, substantially as described.

13. As new products ureids of substituted amino derivatives of aromatic substances characterized by the following formula:

\NHYCONHA in which A stands for the aryl radical of an a romatie substance containing a sulfo group, Y stands for an aromatic radical, forming salts with metals, substantially as described.

14. As new products ureids of substituted amino derivatives of arol'natic substances characterized bythe formula in which A stands for the aryl radical of J described.

15. As new products 'ureids of substituted amino derivatives of aromatic substances characterized by the following formula:

in which A stands for aryl radical of an aromatic substance containing a sulfo group, Y for an aromatic radical, aryl standing for any aromatic radical, forming salts with metals, substantially as described.

16. As new products ureids of substituted amino derivatives of aromatic substances characterized by the following formula:

in which A stands for the aryl radical of an I aromatic substance containing a sulfo group,

salts with metals, substantially as described.

17. As new products ureids of substituted amino derivatives of aromatic substances characterized by the following formula:

forming salts with metals, substantially as described.

19. As a new product the urcid of a sub stituted aminosulfosalicy]ic acid having most probably the formula:

CO-NH-K/JOOIiI QO H BERNHARD HEYMANNQ RICHARD KOTHE. OSKAR DRESSEL. ANTON OSSENBECK. Witnesses:

J. D. ZIESECKEY, J. Ui'mnss- @etteetees in Letters Patent No 1,218 654 It is hereby certified that in Letters Patent No. 1,218,654, granted March 13, 1917 ard Kothe, 0f Upladen, near Cologne, Oskar Dressel, of Miilheim, near Cologne,

upon the application of Bernhard. Heymann, (if Wiesdorf-on-the-Nieden heiri, Richl and. Anton Ossenbeck, of Cologne, Germany, for an improvement in Ureidsend i Thieureids, errors appear in the printedspecifieation requiring eoi'reetion esfolit lows: Page 2, line 68, and page 3, line 6, for the Word sulfonyl reed sulfa; page 1, line 21, formula, for the symbol NIL read N H,,; and that the said Letters Patent should be read With these correetiolis therein that the seme may conform to the resold of the case in the Patent Ufiee. I Signed. and seeleci this 1st day of May, 11., 19170 R; F. WHITEHEAD, Acting Commseihnee 0f Patente 

